EP3350123B1 - Verfahren zur herstellung von borazan - Google Patents

Verfahren zur herstellung von borazan Download PDF

Info

Publication number
EP3350123B1
EP3350123B1 EP16781836.8A EP16781836A EP3350123B1 EP 3350123 B1 EP3350123 B1 EP 3350123B1 EP 16781836 A EP16781836 A EP 16781836A EP 3350123 B1 EP3350123 B1 EP 3350123B1
Authority
EP
European Patent Office
Prior art keywords
borohydride
borazane
gaseous ammonia
ammonia
synthesized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16781836.8A
Other languages
English (en)
French (fr)
Other versions
EP3350123A1 (de
Inventor
Nicolas VANDECANDELAERE
Sébastien COMTE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ArianeGroup SAS
Original Assignee
ArianeGroup SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ArianeGroup SAS filed Critical ArianeGroup SAS
Publication of EP3350123A1 publication Critical patent/EP3350123A1/de
Application granted granted Critical
Publication of EP3350123B1 publication Critical patent/EP3350123B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/14—Compounds containing boron and nitrogen, phosphorus, sulfur, selenium or tellurium
    • C01B35/146—Compounds containing boron and nitrogen, e.g. borazoles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/14—Compounds containing boron and nitrogen, phosphorus, sulfur, selenium or tellurium

Definitions

  • the subject of the present invention is a process for obtaining borazane or ammonia borane of chemical formula NH 3 BH 3 . This process is particularly interesting.
  • borazane is a key to the success of hydrogen generation programs from solid compounds. This generation of hydrogen from solid compounds is currently one of the means proposed to supply fuel cells. In this context, the use of borazane (or ammonia borane) as a solid precursor for the production of hydrogen is already known.
  • the borazane or ammonia borane complex of chemical formula NH 3 BH 3 , which exists in the form of a white crystalline powder, has the unique potential to contain 19.6% by weight of hydrogen. It is thus positioned as a particularly interesting candidate for the solid storage of hydrogen.
  • a borazane synthesis route based on a displacement between a borane (R.BH 3 ) and an amine, typically ammonia, has been widely described, in particular by X. Chen et al in Chem. Eur. J., 2012, 18, 11994-11999 .
  • the most common and most mature synthesis route for borazane is that based on a metathesis (salt) reaction: the reaction of at least one ammonium salt (generally selected from ammonium, ammonium sulfate, ammonium carbonate, ammonium formate and mixtures thereof) with at least one alkali metal borohydride and / or alkaline earth metal (generally selected from lithium borohydride, sodium borohydride) and mixtures thereof), in a solvent, favorably tetrahydrofuran (THF).
  • a solvent favorably tetrahydrofuran
  • the NH 3 BH 3 formed is soluble in said THF. It is separated from the sodium carbonate (co-product) also formed, which precipitates. In fact, at the end of the reaction, the THF solution (thus containing NH 3 BH 3 in solution) is filtered to remove most of the suspended solids. The THF solvent is then evaporated. A powder is finally recovered which essentially contains the desired complex (ammonia borane).
  • THF solvent, THF or equivalent
  • said solvent must be very anhydrous, in order to avoid the production of by-products, particularly that of boron oxides.
  • liquid ammonia is used as the solvent.
  • the use of liquid ammonia undoubtedly weighs down the implementation of the processes in question, as the person skilled in the art is aware that in order to dispose of ammonia in liquid form, it is advisable to operate at a low temperature (below 33 ° C) or under pressure (7-8 bar).
  • these co-liquefactions proceed "successively", so that the at least one borohydride reagent is co-liquefied (with gaseous ammonia) and the borazane formed (as it is formed) is also co-liquefied (with ammonia gas) (see example below).
  • the subject of the present invention is a process for obtaining borazane, comprising the synthesis of said borazane by reacting at least one ammonium salt with at least one borohydride, said at least one borohydride being chosen from alkali metal borohydrides and alkaline earth metal borohydrides.
  • said method is based on a metathesis reaction.
  • Said gaseous ammonia ensures the liquefaction of the at least one borohydride (solid reagent) (by co-liquefaction with said at least one borohydride) ... then that of the synthesized borazane (by co-liquefaction with said synthesized borazane).
  • the gaseous ammonia can be brought into contact with a mixture of at least one borohydride and at least one salt. previously constituted ammonium and that according to another variant (variant B: see below), it may be brought into contact with at least one borohydride, the at least one ammonium salt being then added into the resulting liquid ( co-liquefaction).
  • solids initially the at least one ammonium salt and then less and less of the salt which is consumed and more and more of the -produced product (s).
  • metalthesis reaction the liquid phase of the reaction medium is depleted in the at least one borohydride (co-liquefied) which is consumed and enriched in the borazane which is synthesized and co-liquefied (while the solid phase of said reaction medium is thus depleted in said at least one ammonium salt and is therefore enriched in the (s) co-product (s) of the reaction).
  • the variant B for carrying out the metathesis reaction of the process of the invention can therefore be schematized as follows:
  • ammonia gas does not intervene in the metathesis reaction implemented according to the invention. It intervenes only in "reactions" of solid co-liquefaction / gas.
  • the conduct, according to the invention, of the metathesis reaction under a (permanent) atmosphere of ammonia gas dispenses with the use of any organic solvent (such as THF for example (see above)).
  • organic solvent such as THF for example (see above)
  • the process of the invention is it generally ( a priori always) carried out in the absence of organic solvent.
  • the intervention of such an organic solvent can not be totally excluded from the scope of the invention.
  • Ammonia gas is advantageously used in a molar ratio: ammonia gas / at least one borohydride greater than 1. It is strongly recommended the use of an excess of ammonia. Ammonia gas is in fact advantageously used in a molar ratio greater than 5.
  • reaction metalthesis
  • the at least one ammonium salt is used in excess (relative to the stoichiometry). It is indeed advantageous to exhaust the at least one borohydride reacted with said at least one ammonium salt (the reaction being carried out with the at least one ammonium salt in excess and carried to completion (ie until the depletion of the at least one borohydride)), insofar as it is obviously advantageous, after the reaction, to recover the synthesized borazane as selectively as possible (and with the highest possible yield) .
  • gaseous ammonia for purposes of co-liquefaction with the at least one borohydride, can be brought into contact of said at least one front borohydride (variant B) or after (variant A) the mixture thereof with the at least one ammonium salt.
  • Variant A is preferred in that the prior constitution of the mixture of solid reactants is appropriate for the conduct of the (metathesis) reaction.
  • the at least one ammonium salt is generally selected from ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium chloride, ammonium fluoride, nitrate ammonium, ammonium acetate, ammonium formate, and is preferably ammonium carbonate; and / or, preferably, and said at least one borohydride is generally chosen from sodium borohydride, lithium borohydride and potassium borohydride and advantageously consists of sodium borohydride.
  • the process of the invention thus comprises the reaction (metathesis) between said ammonium carbonate and said sodium borohydride co-liquefied with gaseous ammonia.
  • the reagents used for the implementation of metathesis are advantageously, in a conventional manner, in the form of powders.
  • a powder mixture of at least one ammonium salt with at least one borohydride is produced and the gaseous ammonia is brought into contact with this powder mixture (by sweeping) for co -liquefaction borohydride (s) / gaseous ammonia.
  • the borazane synthesized is, as and when it is synthesized, co-liquefied with gaseous ammonia; and as the progress of the synthesis progresses, the liquid phase of the medium is depleted in co-liquefied borohydride (s) and is enriched in synthesized borazane (also co-liquefied) while the solid phase of said reaction medium is depleted in ammonium salt (s) and is therefore enriched in the (s) co-product (s) of the reaction.
  • the recovery of the synthesized borazane from the reaction medium may also contain a residue of the at least one salt of ammonium (reagent (s)) and / or a residue of the at least one borohydride (other reagent (s)), impurities contained in the reagents and impurities resulting from parasitic reactions) is an operation which should be carried out very advantageously on a reaction medium containing no more borohydride (s) (in any event may contain only a minimum).
  • the recovered borazane is advantageously recovered as pure as possible and conceives the difficulty in separating said synthesized borazane from any borohydride. Therefore, the use of the borazane synthesis according to the invention (metathesis while flushing gaseous ammonia) is strongly favored under conditions which ultimately minimize the presence of borohydride (s), ie it is preferred to use the reaction to completion and with, initially, an excess (advantageously a slight excess) of the at least one ammonium salt relative to the stoichiometry.
  • the depletion of the reaction medium with borohydride (s) can be monitored by analysis of samples, in particular by 1 H NMR.
  • Selective dissolution requires a borazane solvent, non-solvent of the co-product (s) of the synthesis (it is understood that the co-product is sodium carbonate when sodium borohydride and ammonium carbonate are used as reagents and co-products are generally generated when at least two ammonium salts and / or at least two borohydrides are used as reagents) and the remainder of the at least one ammonium salt.
  • a solvent may especially consist of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, acetonitrile, ethyl acetate, isopropyl acetate, dimethyl carbonate or a mixture thereof.
  • reaction completed any supply of ammonia gas being of course stopped (ie the ammonia gas sweep being stopped) and started with an excess of the at least one ammonium salt
  • reaction completed any supply of ammonia gas being of course stopped (ie the ammonia gas sweep being stopped) and started with an excess of the at least one ammonium salt
  • the reaction medium is filtered to remove solids (mainly the (the) co-product (s) of the synthesis and the remainder of the at least one salt of ammonium used in excess); and 2) the ammonia is removed (by evaporation, advantageously by evaporation in vacuo, with reference to the kinetics); said elimination of ammonia causing the precipitation of a solid phase consisting almost exclusively (or exclusively) of synthesized borazane (in the absence, a priori any residue of borohydride (s)).
  • the metathesis reaction was carried out in a three-necked flask (with a volume of 100 ml), equipped with stirring means.
  • An ice bath was set up under said three-necked flask to ensure a temperature of 0 ° C in the volume of said three-necked flask.
  • a flow of gaseous ammonia (about 45 mL / min) was then introduced, by one of the necks of the flask, at atmospheric pressure.
  • the gaseous ammonia introduced, not liquefied, was evacuated by another neck of the balloon.
  • the borazane thus synthesized was then recovered by selective dissolution from said solid (of said powder).
  • 2-Methyltetrahydrofuran (50 mL) was introduced into said flask on the solid.
  • Said 2-methyltetrahydrofuran provided selective dissolution of borazane; hence obtaining a solid phase dispersed in a liquid phase containing said borazane dissolved in said 2-methyltetrahydrofuran.
  • This solid phase - consisting essentially of the product obtained together with borazane (co-product: Na 2 CO 3 ) and excess of (NH 4 ) 2 CO 3 , mainly of the product obtained together with borazane (co-product: Na 2 CO 3 ) - was removed by filtration.
  • the synthesized borazane dissolved in 2-methyltetrahydrofuran was then recovered by evaporation of said 2-methyltetrahydrofuran (evaporation carried out at 30 ° C under 100 mbar for 1 h).
  • Borazane, synthesized according to the invention also had an interesting degree of purity.
  • the presence of impurities at detectable levels has not been demonstrated by 1 H NMR (a given mass of the synthesized borazane has been dissolved in a solvent (THF), benzene being added to the solution analyzed as standard), or by infra-red, ie that any impurity potentially present was only at a rate lower than 1% by mass (in fact, according to the infrared technique, any impurity potentially present does not was at a rate well below 1% by mass).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)

Claims (12)

  1. Verfahren zum Erhalten von Borazan, umfassend die Synthese des Borazans durch eine Reaktion von mindestens einem Ammoniumsalz mit mindestens einem Borhydrid, wobei das mindestens eine Borhydrid ausgewählt ist aus den Borhydriden eines Alkalimetalls und den Borhydriden eines Erdalkalimetalls, dadurch gekennzeichnet, dass die Reaktion unter Spülung von gasförmigem Ammoniak umgesetzt wird, wobei das gasförmige Ammoniak mit dem mindestens einen Borhydrid und nach und nach bei seiner Synthese mit dem Borazan gemeinsam verflüssigt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Reaktion bei einem Druck zwischen 1. 105 und 2. 105 Pa (1 und 2 atm), vorteilhafterweise bei Atmosphärendruck, und bei einer Temperatur zwischen -5 °C und 25 °C umgesetzt wird.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Reaktion in Abwesenheit eines organischen Lösungsmittels umgesetzt wird.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das gasförmige Ammoniak in einem Molverhältnis verwendet wird: gasförmiges Ammoniak/mindestens ein Borhydrid größer als 1, vorteilhafterweise größer als 5.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das mindestens eine Ammoniumsalz in Bezug auf die Stöchiometrie im Überschuss, vorteilhafterweise mit einem leichten Überschuss, verwendet wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es umfasst:
    - Bildung eines Gemischs des mindestens einen Ammoniumsalzes mit dem mindestens einen Borhydrid,
    - Umsetzung einer Spülung von gasförmigem Ammoniak zum In-Kontakt-Bringen des Gemischs mit dem gasförmigen Ammoniak, wobei das gasförmige Ammoniak dann mit dem mindestens einen Borhydrid gemeinsam verflüssigt ist, und
    - Reaktion des mindestens einen gemeinsam verflüssigten Borhydrids und des mindestens einen Ammoniumsalzes unter Spülung von gasförmigem Ammoniak, wobei das synthetisierte Borazan nach und nach bei seiner Synthese mit dem gasförmigen Ammoniak gemeinsam verflüssigt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es umfasst:
    - Umsetzung einer Spülung von gasförmigem Ammoniak zum In-Kontakt-Bringen des mindestens einen Borhydrids mit dem gasförmigen Ammoniak, wobei das gasförmige Ammoniak mit dem mindestens einen Borhydrid gemeinsam verflüssigt ist,
    - Zugabe des mindestens einen Ammoniumsalzes zu dem mindestens einen mit dem gasförmigen Ammoniak gemeinsam verflüssigten Borhydrid, und
    - Reaktion des mindestens einen gemeinsam verflüssigten Borhydrids und des mindestens einen Ammoniumsalzes unter Spülung von gasförmigem Ammoniak, wobei das synthetisierte Borazan nach und nach bei seiner Synthese mit dem gasförmigen Ammoniak gemeinsam verflüssigt wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das mindestens eine Ammoniumsalz aus Ammoniumcarbonat, Ammoniumbicarbonat, Ammoniumsulfat, Ammoniumchlorid, Ammoniumfluorid, Ammoniumnitrat, Ammoniumacetat, Ammoniumformiat ausgewählt ist und vorteilhafterweise aus Ammoniumcarbonat besteht, und/oder vorzugsweise und dadurch, dass das mindestens eine Borhydrid aus Natriumborhydrid, Lithiumborhydrid und Kaliumborhydrid ausgewählt ist und vorteilhafterweise aus Natriumborhydrid besteht.
  9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass es ferner nach der Reaktion umfasst:
    - Stoppen der Spülung von gasförmigem Ammoniak,
    - Eliminierung des Ammoniaks, vorzugsweise durch eine Verdampfung im Vakuum, wobei die Eliminierung des Ammoniaks die Ausfällung einer festen Phase verursacht, in der das synthetisierte Borazan enthalten ist, und
    - selektive Auflösung des synthetisierten Borazans in einem Lösungsmittel und anschließend Eliminierung des Lösungsmittels für die Rückgewinnung des synthetisierten Borazans durch eine Verdampfung im Vakuum.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass das Lösungsmittel aus Tetrahydrofuran, 2-Methyltetrahydrofuran, Dioxan, Acetonitril, Ethylacetat, Isopropylacetat, Dimethylcarbonat und einem ihrer Gemische ausgewählt ist.
  11. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass es ferner nach der Reaktion umfasst:
    - Stoppen der Spülung von gasförmigem Ammoniak,
    - Filtration des Reaktionsmediums für die Eliminierung der Feststoffe,
    - Eliminierung des Ammoniaks, vorzugsweise durch eine Verdampfung im Vakuum, wobei die Eliminierung des Ammoniaks die Ausfällung einer festen Phase verursacht, die fast ausschließlich durch das synthetisierte Borazan gebildet wird.
  12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass es umfasst:
    - Bildung eines pulverförmigen Gemischs des mindestens einen Ammoniumsalzes mit dem mindestens einen Borhydrid, wobei das mindestens eine Ammoniumsalz in Bezug auf die Stöchiometrie mit einem leichten Überschuss verwendet wird,
    - Umsetzung einer Spülung von gasförmigem Ammoniak zum In-Kontakt-Bringen des Gemischs mit dem gasförmigen Ammoniak, dann nach der Reaktion,
    - Stoppen der Spülung von gasförmigem Ammoniak,
    - Eliminierung des Ammoniaks, vorzugsweise durch eine Verdampfung im Vakuum, wobei die Eliminierung des Ammoniaks eine feste Phase erzeugt, in der das synthetisierte Borazan enthalten ist, und
    - selektive Auflösung des synthetisierten Borazans in einem Lösungsmittel und anschließend Eliminierung des Lösungsmittels für die Rückgewinnung des synthetisierten Borazans durch eine Verdampfung im Vakuum.
EP16781836.8A 2015-09-18 2016-09-16 Verfahren zur herstellung von borazan Active EP3350123B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1558803A FR3041338B1 (fr) 2015-09-18 2015-09-18 Procede d'obtention du borazane
PCT/FR2016/052349 WO2017046540A1 (fr) 2015-09-18 2016-09-16 Procede d'obtention du borazane.

Publications (2)

Publication Number Publication Date
EP3350123A1 EP3350123A1 (de) 2018-07-25
EP3350123B1 true EP3350123B1 (de) 2019-05-29

Family

ID=56137374

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16781836.8A Active EP3350123B1 (de) 2015-09-18 2016-09-16 Verfahren zur herstellung von borazan

Country Status (4)

Country Link
US (1) US20180251380A1 (de)
EP (1) EP3350123B1 (de)
FR (1) FR3041338B1 (de)
WO (1) WO2017046540A1 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009532469A (ja) * 2006-04-03 2009-09-10 ザ オハイオ ステイト ユニバーシティ アンモニアボランの合成方法
US20100272623A1 (en) * 2009-04-22 2010-10-28 K-Energetics Corp. Ambient temperature liquid ammonia process for the manufacture of ammonia borane
FR3021317B1 (fr) * 2014-05-23 2016-06-17 Herakles Procede d'obtention du borazane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
US20180251380A1 (en) 2018-09-06
WO2017046540A1 (fr) 2017-03-23
FR3041338B1 (fr) 2019-05-10
FR3041338A1 (fr) 2017-03-24
EP3350123A1 (de) 2018-07-25

Similar Documents

Publication Publication Date Title
CA2800306C (fr) Procede d'obtention de borazane, convenant pour l'obtention de borazane de grande purete, voire de tres grande purete
US20220204353A1 (en) Method for Synthesizing Ammonia, and Apparatus for Said Method
FR2552416A1 (fr) Procede de preparation de trifluorure d'azote par reaction gaz-solide
JP6709686B2 (ja) ビス（フルオロスルホニル）イミドアルカリ金属塩の製造方法
CA2878050A1 (fr) Procede de preparation d'un compose sulfonimide et de ses sels
EP3145863B1 (de) Verfahren zur herstellung von borazan
WO2017046540A1 (fr) Procede d'obtention du borazane.
US11608274B2 (en) Alkali metal cyanide production
EP0230686B1 (de) Verfahren zur Herstellung einer wässrigen Natriumchloridlösung und Verfahren zur Erzeugung von Natriumbikarbonat
FR3021317A1 (fr) Procede d'obtention du borazane
KR102946454B1 (ko) 알칸의 정제를 위한 방법
EP3350122B1 (de) Verfahren zur reinigung von borazan
WO2012140371A1 (fr) Procede de preparation d'alkyltetrazenes
JP2014234318A (ja) アルカリ金属硫化物の製造方法
LU85506A1 (fr) Procede pour la preparation d'une solution aqueuse de chlorure de sodium et procede de fabrication de bicarbonate de sodium
JP2009292757A (ja) スルホキシド化合物の製造法
CA2550080C (fr) Procede de synthese de derives de cycloalkyl-hydrazines exocycliques et de derives d`heterocycloalkyl-hydrazines exocycliques
JPH0353244B2 (de)
WO2014167226A1 (fr) Obtention de solutions d'ota en milieu acide sulfurique concentre; lesdites solutions; preparation d'onta.
BE541940A (de)

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180316

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190107

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1138148

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190615

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016014623

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190529

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190930

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190829

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190830

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190829

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1138148

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016014623

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

26N No opposition filed

Effective date: 20200303

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190930

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190930

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190916

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190916

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20200910

Year of fee payment: 5

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200916

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160916

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200916

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602016014623

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220401

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230612

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250922

Year of fee payment: 10